Detergent mixtures containing oligomeric esterquats

ABSTRACT

Detergent mixtures comprising (a) an oligomeric esterquat which is the product of the process which comprises reacting a mixture of a mono-carboxylic acid and a dicarboxylic acid with an alkanolamine to form an alkanolamine oligoester and reacting the alkanolamine oligoester with an alkylating agent and (b) the product of the process which comprises reacting an alkylene oxide and a fatty acid amidoamine, wherein the weight ratio of components (a) to (b) is from about 10:90 to about 90:10; and wherein the oligomeric esterquat has at least two cationic centers.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to detergent mixtures containing oligomericesterquats and alkoxylated fatty acid amidoamines and to the use of themixtures for the production of fabric softeners and hair-carecompositions.

2. Statement of Related Art

As a result of increased biodegradability requirements, quaternary fattyacid alkanolamine ester salts, so-called “esterquats”, have displacedtetraalkyl ammonium compounds as cationic surfactants both for theproduction of fabric softeners and for the conditioning of hair.Overviews on this subject have been published, for example, by R. Puchtaet al. in Tens. Surf. Det., 30, 186 (1993), by M. Brock in Tens. Surf.Det. 30, 394 (1993), by R. Lagerman et al. in J. Am. Oil. Chem. Soc.,71, 97 (1994) and by l. Shapiro in Cosm. Toil. 109, 77 (1994). However,there is a demand on the market for products with further improvedproperties.

Accordingly, the complex problem addressed by the present invention wasto provide detergent mixtures which would have improved conditioning andantistatic properties and complete biological degradability, could bedissolved quickly and completely, even in cold water, would have asufficiently high viscosity but would not thicken or form gels instorage and, finally, would dissolve clearly in any ratio with waterwithout any need for alcohols.

DESCRIPTION OF THE INVENTION

The present invention relates to detergent mixtures containing

(a) oligomeric esterquats obtainable by condensation of mixtures ofmono-and dicarboxylic acids with alkanolamines and subsequentquaternization of the alkanolamine oligoesters and

(b) products of the addition of alkylene oxides onto fatty acidamidoamines.

It has surprisingly been found that the mixtures according to theinvention not only are highly concentrated and water-clear, they alsohave an advantageously high and stable viscosity. The preparations canbe diluted with water in any quantities and may then be immediately usedas fabric softeners or hair-care compositions. They provide bothsynthetic and natural fibers with a particularly pleasant soft feel and,in addition, reduce the static charging between the fiber filaments to aquite considerable extent. Another advantage is that they can bedispersed particularly easily in cold water and, in addition, arereadily biodegradable.

Oligomeric esterguats

The oligomeric esterquats have at least two cationic centers and,accordingly, differ from other known esterquats which have only onequaternary nitrogen. The production and use of these substances is knownfrom DE-C1 19539846 (Henkel). In simple terms, the synthesis principleconsists in linking several, but preferably exactly two, polyfunctionalalkanolamines by means of a dicarboxylic acid, completely or partlyesterifying the free hydroxyl groups with monocarboxylic acids and thenquatemizing the nitrogen atoms present in the oligomeric or dimericester by methods known per se.

Typical examples of monocarboxylic acids, which may be used as one ofthe two acid components of the oligomeric esterquats, are fatty acidsand oxocarboxylic acids containing 6 to 22 carbon atoms such as, forexample, caproic acid, caprylic acid, 2-ethyl hexanoic acid, capricacid, lauric acid, isotridecanoicacid, myristic acid, palmitic acid,palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidicacid, petroselic acid, linoleic acid, linolenic acid, elaeostearic acid,arachic acid, gadoleic acid, behenic acid and erucic acid and thetechnical mixtures thereof obtained, for example, in the pressurehydrolysis of natural fats and oils, in the reduction of aldehydes fromRoelen's oxosynthesis or in the dimerization of unsaturated fatty acids.Technical fatty acids containing 12 to 18 carbon atoms, for examplecoconut, palm, palm kernel or tallow acid, preferably in hydrogenated orpartly hydrogenated form, are preferred. Examples of suitabledicarboxylic acids, which may be used as a second bridging carboxylicacid component, are succinic acid, maleic acid, glutaric acid,1,12-dodecanedioic acid and, more particularly, adipic acid. Oligomericesterquats based on fatty acids containing 6 to 22 carbon atoms andadipic acid are preferably used. To produce the oligomeric esterquats,the mono-and dicarboxylic acids may be used in a molar ratio of 1:1 to3:1 and preferably 1.5:1 to 2.5:1.

The alkanolamine component of the oligomeric esterquats may be derivedfrom methyl diethanolamine, but is preferably derived fromtri-ethanolamine and from mixtures of the two. To produce the compounds,the mono-/dicarboxylic acids on the one hand and the alkanolamines onthe other hand may be used in a molar ratio of 1:1 to 3:1 and arepreferably used in a molar ratio of 1.5:1 to 2:1.

The esterification may be carried out in known manner, as described forexample in International patent application WO 91101295 (Henkel). Theesterification is advantageously carried out at temperatures of 120 to220° C. and, more particularly, 130 to 170° C. and under pressures of0.01 to 1 bar. Suitable catalysts are hypophosphorous acid and alkalimetal salts thereof, preferably sodium hypophosphite, which may be usedin quantities of 0.01 to 0.1% by weight and are preferably used inquantities of 0.05 to 0.07% by weight, based on the starting materials.In the interests of 30 particularly high color quality and stability, ithas proved to be of advantage to use alkali metal and/or alkaline earthmetal borohydrides such as, for example, potassium, magnesium and inparticular sodium borohydride. The co-catalysts are normally used inquantities of 50 to 1000 ppm and more particularly 100 to 500 ppm, againbased on the starting materials. Corresponding processes are also thesubject of German patents DE-C1 4308792 and DE-C1 4409322 (Henkel), towhich reference is specifically made here. Mixtures of the fatty acidsand dicarboxylic acids may be used or the esterification may be carriedout with the two components in succession.

The quaternization of the fatty acid/dicarboxylic acid alkanolamineesters may be carried out in known manner. Although the reaction withthe alkylating agents can be carried out in the absence of solvents, itis advisable to use at least small quantities of water or loweralcohols, preferably isopropyl alcohol, for the preparation ofconcentrates which have a solids content of at least 80% by weight and,more particularly, at least 90% by weight. Suitable alkylating agentsare alkyl halides, for example methyl chloride; dialkyl sulfates, forexample dimethyl sulfate or diethyl sulfate; or dialkyl carbonates suchas, for example, dimethyl carbonate or diethyl carbonate. The esters andthe alkylating agents are normally used in a molar ratio of 1:0.95 to1:1.05, i.e. in a substantially stoichiometric ratio. The reactiontemperature is normally in the range from 40 to 80° C. and moreparticularly in the range from 50 to 60° C. After the reaction, it isadvisable to destroy unreacted alkylating agent by addition of, forexample, ammonia, an (alkanol)amine, an amino acid or an oligopeptide,as described for example in German patent application DE-A1 4026184(Henkel).

In the reaction of the alkanolamines with the mixtures of mono-anddicarboxylic acids, complex mixtures predominantly containing dimers,i.e. species in which two alkanolamines are bridged by a dicarboxylicacid and of which the free hydroxyl groups are partly esterified withmonocarboxylic acids, are obtained. According to gel permeationchromatography, the mixtures also contain oligomeric esters where 3 to 4quaternary centers are present. Monomeric compounds containing only onequaternary nitrogen are undesirable for performance-related reasonsbecause they adversely affect clear solubility. Although they cannot becompletely prevented from occurring, their content can be reduced tobelow 5% by weight through the presence of a sufficient quantity ofdicarboxylic acid. The dimeric compounds corresponding to formula (I):

in which R¹CO is an aliphatic, linear or branched, saturated orunsaturated acyl group containing 6 to 22 corbon atome, R² is an alkylgroup containing 1 to 4 carbon atoms, R³ and R⁵ independently of onenother represent alkyl or hydroxyalkyl groups containing 1 to 4 carbonatoms, R⁴ is hydrogen or has the same meaning as R¹ CO, n1, n2, n3 andn4 independently of one another have a value of 1 to 5 and m has a valueof 1 to 10. Dimeric esterquats with particularly advantageous propertiescorrespond to formula (I) where R¹CO is a linear saturated acyl groupcontaining 12 to 18 carbon atoms, R²is a methyl group, R³ and R⁵ eachrepresent hydroxyethyl groups, R⁴ has the same meaning as R¹ CO n1, n2,n3 and n4 each have a value of 2 and m has a value of 4. The oligomericesterquats preferably contain 20 to 90% by weight and more preferably 40to 80% by weight of dimers, 10 to 80% by weight and more preferably 20to 60% by weight of oligomers and less than 5% by weight of monomers,with the proviso that the quantities mentioned add up to 100% by weight.

Alkoxylated Fatty Acid Amidoamines

Alkoxylation products of fatty acid amidoamines are also known from theliterature and preferably correspond to formula (II):

in which R⁶CO is an aliphatic, linear or branched, saturated orunsaturated. acyl group containing 6 to 22 carbon atoms, R⁷and R⁸independently of one another represent hydrogen or an optionallyhydroxysubstituted alkyl group containing 1 to 4 carbon atoms, R⁹ ishydrogen, an alkyl group containing 1 to 4 carbon atoms or has the samemeaning as R⁶CO, R¹⁰ and R¹¹ independently of one another representhydrogen or a methyl group, A is a linear or branched alkylene groupcontaining 2 to 4 carbon atoms, p and q independently of one anotherhave a value of 1 to 3, y has a value of 1 to 3 and z has a value of 1to 20.

They are normally produced from dialkylenetriamines ortrialkylene-tetramines which are first esterified with 1 to 2 moles ofcarboxylic acid and then reacted in known manner with alkylene oxides,preferably ethylene oxide, for insertion into the free NH bonds. Typicalexamples of suitable oligoamines are diethylenetriamine,dipropylenetriamine, triethylene-tetramine and tripropylenetetramine andmixtures thereof. Suitable car-boxylic acids are the fatty acidscontaining 6 to 22 carbon atoms such as, for example, caproic acid,caprylic acid, 2-ethyl hexanoic acid, capric acid, lauric acid,isotridecanoic acid, myristic acid, palmitic acid, paimitoleic acid,stearic acid, isostearic acid, oleic acid, elaidic acid, petroselicacid, linoleic acid, linolenic acid, elaeostearic acid, arachic acid,gadoleic acid, behenic acid and emucic acid and the technical mixturesthereof obtained, for example, in the pressure hydrolysis of naturalfats and oils, in the reduction of aldehydes from Roelen's oxosynthesisor in the dimerization of unsaturated fatty acids. Technical fatty acidscontaining 12 to 18 carbon atoms, for example coconut, palm, palm kernelor tallow acid, preferably in hydrogenated or partly hydrogenated form,are preferred. It has proved to be of particular advantage to use thecarboxylic acids in such quantities that, on average, diamides areobtained. In addition, alkoxylated fatty acid amidoamines correspondingto formula (II), where R⁶CO is a linear saturated acyl group containing12 to 18 carbon atoms, R⁷, R⁸, R¹⁰ and R¹¹ represent hydrogen, R⁹ hasthe same meaning as R⁶CO, A is an ethylene group, p and q each have avalue of 2, y has a value of 1 and z has a vlaue of 5 to 10, areparticularly preferred for applicational reasons.

The alkoxylation may be carried out in known manner, i.e. ethyleneoxide, propylene oxide or mixtures thereof are added in the presence ofacidic, but preferably basic catalysts, for example sodium methylate orcalcined hydrotalcite. Nonionic compounds are formed, but are quicklyprotonated in acidic solution and then show pseudocationic behavior.

According to the invention, the detergent mixtures may containcomponents (a) and (b) in a ratio by weight of 10:90 to 90:10,preferably 25:75 to 75:25 and more preferably 40:60 to 60:40.

Commercial Applications

The present invention also relates to the use of the detergent mixturesfor the production of fabric softeners and hair-care preparations inwhich they may be present in quantities of 1 to 50% by weight,preferably 5 to 35% by weight and more preferably 10 to 25% by weight.Apart from the possibility of directly using the mixtures for the statedpurpose, the most simple form of use consists in diluting them withwater to the required in-use concentration.

Surfactants

In this connection, other additives, more particularly othersurfactants, which are compatible with components (a) and (b) may alsobe added to the preparations. The surfactants in question are, aboveall, other nonionic or cationic or amphoteric or zwitterionicsurfactants. Typical examples of nonionic surfactants are fatty alcoholpolyglycol ethers, alkylphenol polyglycol ethers, fatty acid polyglycolesters, fatty acid amide polyglycol ethers, fatty amine polyglycolethers, alkoxylated triglycerides, mixed ethers and mixed formals,optionally partly oxidized alk(en)yl oligoglycosides or glucuronic acidderivatives, fatty acid-N-alkyl glucamides, protein hydrolyzates(particularly wheat-based vegetable products), polyol fatty acid esters,sugar esters, sorbitan esters, polysor-bates and amine oxides. If thenonionic surfactants contain polyglycol ether chains, they may have aconventional homolog distribution, although they preferably have anarrow-range homolog distribution. Typical examples of cationicsurfactants are quaternary ammonium compounds and monomeric esterquats,more particularly quaternized fatty acid trialkanolamine ester salts.Typical examples of amphoteric or zwifterionic surfactants arealkylbetaines, alkylamidobetaines, amino-propionates, aminoglycinates,imidazolinium betaines and sulfobetaines. The surfactants mentioned areall known compounds. Information on their structure and production canbe found in relevant synoptic works, cf. for example J. Falbe (ed.),“Surfactants in Consumer Products”, Springer Verlag, Berlin, 1987, pages54 to 124 or J. Falbe (ed.), “Katalysatoren, Tenside undMineraldladditive (Catalysts, Surfactants and Mineral Oil Additives)”,Thieme Verlag, Stuttgart, 1978, pages 123-217.

Auxiliaries and additives

Depending on the application envisaged, i.e. fabric softening or hairconditioning, the preparations obtainable using the detergent mixturesmay contain other typical auxiliaries and additives, such as oilcomponents, emulsifiers, superfatting agents, pearlizing waxes,stabilizers, consistency factors, thickeners, cationic polymers,silicone compounds, biogenic agents, antidandruff agents, film formers,preservatives, hydrotropes, solubilizers, UV filters, insect repellents,self-tanning agents, perfume oils, dyes and the like.

Suitable oil components are, for example, Guerbet alcohols based onfatty alcohols containing 6 to 18 and preferably 8 to 10 carbon atoms,esters of linear C₆₋₂₂ fatty acids with linear C₆₋₂₂ fatty alcohols,esters of branched C₆₋₂₂ carboxylic acids with linear C₆₋₂₂ fattyalcohols, esters of linear C₆₋₂₂ fatty acids with branched alcohols,more particularly 2-ethyl hexanol, esters of linear and/or branchedfatty acids with polyhydric alcohols (for example propylene glycol,dimer diol or trimer triol) and/or Guerbet alcohols, triglycerides basedon C₆₋₁₀ fatty acids, liquid mono-/di-/triglyceride mixtures based onC₆₋₁₈ fatty acids, esters of C₆₋₂₂ fatty alcohols and/or Guerbetalcohols with aromatic carboxylic acids, more particularly benzoic acid,vegetable oils, branched primary alcohols, substituted cyclohexanes,linear C₆₋₂₂ fatty alcohol carbonates, Guerbet carbonates, esters ofbenzoic acid with linear and/or branched C₆₋₂₂ alcohols (for exampleFinsolv® TN), dialkyl ethers, ring opening products of epoxidized fattyacid esters with polyols, silicone oils and/or aliphatic or naphthenichydrocarbons.

Suitable emulsifiers are, for example, nonionic surfactants from atleast one of the following groups:

(1) products of the addition of 2 to 30 moles of ethylene oxide and/or 0to 50 moles of propylene oxide onto linear fatty alcohols containing 8to 22 carbon atoms, onto fatty acids containing 12 to 22 carbon atomsand onto alkylphenols containing 8 to 15 carbon atoms in the alkylgroup;

(2) C_(12/18) fatty acid monoesters and diesters of addition products of1 to 30 moles of ethylene oxide onto glycerol;

(3) glycerol monoesters and diesters and sorbitan monoesters anddiesters of saturated and unsaturated fatty acids containing 6 to 22carbon atoms and ethylene oxide adducts thereof;

(4) alkyl mono- and oligoglycosides containing 8 to 22 carbon atoms inthe alkyl group and ethoxylated analogs thereof;

(5) addition products of 15 to 60 moles of ethylene oxide onto castoroil and/or hydrogenated castor oil;

(6) polyol esters and, in particular, polyglycerol esters such as, forexample, polyglycerol polyricinoleate, polyglycerolpoly-12-hydroxy-istearate or polyglycerol dimerate. Mixtures ofcompounds from several of these classes: are also suitable;

(7) addition products of 2 to 15 moles of ethylene oxide onto castor oiland/or hydrogenated castor oil;

(8) partial esters based on linear, branched, unsaturated or saturatedC_(6/22) fatty acids, ricinoleic acid and 12-hydroxystearic acid andglycerol, polyglycerol, pentaerythritol, dipentaerythritol, sugaralcohols (for example sorbitol), alkyl glucosides (for example methylglucoside, butyl glucoside, lauryl glucoside) and polyglucosides (forexample cellulose);

(9) mono-, di and trialkyl phosphates and mono-, di- and/ortri-PEG-alkyl phosphates;

(10) wool wax alcohols;

(11) polysiloxanelpolyalkyl polyether copolymers and correspondingderivatives;

(12) mixed esters of pentaerythritol, fatty acids, citric acid and fattyalcohol according to DE-PS 11 65 574 and/or mixed esters of fatty acidscontaining 6 to 22 carbon atoms, methyl glucose and polyols, preferablyglycerol, and

(13) polyalkylene glycols.

The addition products of ethylene oxide and/or propylene oxide ontofatty alcohols, fatty acids, alkylphenols, glycerol monoesters anddiesters and sorbitan monoesters and diesters of fatty acids or ontocastor oil are known commercially available products. They are homologmixtures of which the average degree of alkoxylation corresponds to theratio between the quantities of ethylene oxide and/or propylene oxideand substrate with which the addition reaction is carried out. C_(2/18)fatty acid monoesters and diesters of addition products of ethyleneoxide onto glycerol are known as refatting agents for cosmeticformulations from DE-PS 20 24 051.

C_(8/18) alkyl mono- and oligoglycosides, their production and their useas surfactants are known from the prior-art literature. They areproduced in particular by reacting glucose or oligosaccharides withprimary alcohols containing 8 to 18 carbon atoms. So far as theglycoside component is concerned, both monoglycosides where a cyclicsugar unit is attached to the fatty alcohol by a glycoside bond andoligomeric glycosides with a degree of oligomerization of preferably upto about 8 are suitable. The degree of oligomerization is a statisticalmean value on which a homolog distribution typical of such technicalproducts is based.

Other suitable emulsifiers are zwitterionic surfactants. Zwitterionicsurfactants are surface-active compounds which contain at least onequaternary ammonium group and at least one carboxylate and one sulfonategroup in the molecule. Particularly suitable zwitterionic surfactantsare the so-called betaines, such as the N-alkyl-N,N-dimethyl ammoniumglycinates, for example coconutalkyl dimethyl ammonium glycinate,N-acylaminopropyl-N,N-dimethyl ammonium glycinates, for examplecoconutacylaminopropyl dimethyl ammonium glycinate, and2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazolines containing 8 to 18carbon atoms in the alkyl or acyl group and coconutacylaminoethylhydroxyethyl carboxymethyl glycinate. The fatty acid amide derivativeknown under the CTFA name of Cocamidopropyl Betaine is particularlypreferred. Ampholytic surfactants are also suitable emulsifiers.Ampholytic surfactants are surface-active compounds which, in additionto a C_(8/18) alkyl or acyl group, contain at least one free amino groupand at least one —COOH— or —SO₃H— group in the molecule and which arecapable of forming inner salts. Examples of suitable ampholyticsurfactants are N-alkyl glycines, N-alkyl propionic acids,N-alkylaminobutyric acids, N-alkyliminodipropionic acids,N-hydroxyethyl-N-alkylamidopropyl glycines, N-alkyl taurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acidscontaining around 8 to 18 carbon atoms in the alkyl group. Particularlypreferred ampholytic surfactants are N-coconut-alkylaminopropionate,cocoacylaminoethyl aminopropionate and C_(12/18) acylsarcosine.According to the invention, other suitable emulsifiers besidesampholytic surfactants are quaternary emulsifiers, those of theesterquat type, preferably. methyl-quatemized difatty acidtriethanolamine ester salts, being particularly preferred.

Superfaffing agents may be selected from such substances as, forexample, lanolin and lecithin and also polyethoxylated or acylatedlanolin and lecithin derivatives, polyol fatty acid esters,monoglycerides and fatty acid alkanolamides, the fatty acidalkanolamides also serving as foam stabilizers.

Suitable pearlizing waxes are, for example, alkylene glycol esters,particularly ethylene glycol distearate; fatty acid: alkanolamides,especially coconut acid diethanolamide; partial glycerides,: especiallystearic acid monoglyceride; esters of polybasic, optionallyhydroxysubstituted carboxylic acids with fatty alcohols containing 6 to22 carbon atoms, especially long-chain esters of tartaric acid; fattycompounds, for example fatty alcohols, fatty ketones, fatty aldehydes,fatty ethers and fatty carbonates which contain a total of at least 24carbon atoms, especially laurone and distearyl ether; fatty acids, suchas stearic acid, hydroxystearic acid or behenic acid, ring openingproducts of olefin epoxides containing 12 to 22 carbon atoms with fattyalcohols containing 12 to 22 carbon atoms and/or polyols containing 2 to15 carbon atoms and 2 to 10 hydroxyl groups; and mixtures thereof.

The consistency factors mainly used are fatty alcohols containing 12 to22 and preferably 16 to 18 carbon atoms and also partial glycerides. Acombination of these substances with alkyl oligoglucosides and/or fattyacid-N-methyl glucamides of the same chain length and/or polyglycerolpoly-12-hydroxystearates is preferably used. Suitable thickeners are,for example, polysaccharides, more especially xanthan gum, guar-guar,agar-agar, alginates and tyloses, carboxymethyl cellulose andhydroxyethyl cellulose, also relatively high molecular weightpolyethylene glycol mono-esters and diesters of fatty acids,polyacrylates (for example Carbopols® [Goodrichl] or Synthalens®[Sigma]), polyacrylamides, polyvinyl alcohol and polyvinyl pyrrolidone,surfactants such as, for example, ethoxylated fatty acid glycerides,esters of fatty acids with polyols, for example pentaerythritol ortrimethylol propane, narrow-range fatty alcohol ethox-ylates or alkyloligoglucosides and electrolytes, such as sodium chloride and ammoniumchloride.

Suitable cationic polymers are, for example, cationic cellulosederivatives such as, for example, the quaternized hydroxyethyl celluloseobtainable from Amerchol under the name of Polymer JR 400®, cationicstarch, copolymers of diallyl ammonium salts and acrylamides, quatemizedvinyl pyrrolidone/vinyl imidazole polymers such as, for example,Luviquato (BASF), condensation products of polyglycols and amines,quatemized collagen polypeptides such as, for example, LauryidimoniumHydroxypropyl Hydrolyzed Collagen (Lamequat®L/Grinau), quaternized wheatpolypeptides, polyethyleneimine, cationic silicone polymers such as, forexample, amodimethicone, copolymers of adipic acid and dimethylaminohydroxypropyl diethylenetriamine (Cartaretine®/Sandoz), copolymers ofacrylic acid with dimethyl diallyl ammonium chloride (Merquat® 550/Chemviron), polyaminopolyamides as described, for example, in FR-A 2 252840 and crosslinked water-soluble polymers thereof, cationic chitinderivatives such as, for example, quatemized chitosan, optionally inmicro-crystalline distribution, condensation products of dihaloalkys,for example dibromobutane, with bis-dialkylamines, for examplebis-dimethylamino-1,3-propane, cationic guar gum such as, for example,Jaguar®CBS, Jaguar®C-17, Jaguar®C-16 of Celanese, USA, quatemizedammonium salt polymers such as, for example, Mirapol® A-15, Mirapol®AD-1, Mirapol® AZ-1 of Miranol, USA.

Suitable silicone compounds are, for example, dimethyl polysilox-anes,methylphenyl polysiloxanes, cyclic silicones and amino-, fattyacid-,alcohol-, polyether-, epoxy-, fluorine-, glycoside- and/oralkyl-modified silicone compounds which may be both liquid andresin-like at room temperature. Typical examples of fats are glycerideswhile suitable waxes are inter alia beeswax, camauba wax, candelillawax, montan wax, paraffin wax or microwaxes, optionally in combinationwith hydrophilic waxes, for example cetyl stearyl alcohol or partialglycerides. Metal salts of fatty acids such as, for example, magnesium,aluminium and/or zinc stearate or ricinoleate may be used asstabilizers. In the context of the invention, biogenic agents are, forexample, tocopherol, tocopherol acetate, tocopherol palmitate, ascorbicacid, deoxyribonucleic acid, retinol, bisabolol, allantoin, phytantriol,panthenol, AHA acids, amino acids, ceramides, pseudoceramides, essentialoils, plant extracts, proteolytic enzymes and, vitamin complexes.Suitable antidandruff agents are climbazol, octopirox and zincpyrithione. Typical film formers are, for example, chitosan,microcrystalline chitosan, quatemized chitosan, polyvinyl pyrrolidone,vinyl pyrrolidone/vinyl acetate copolymers, polymers of the acrylic acidseries, quaternary cellulose derivatives, collagen, hyaluronic acid andsalts thereof and similar compounds. Suitable swelling agents foraqueous phases include montmorillonites, clay minerals, Pemulen andalkyl-modified Carbopol types (Goodrich).

UV filters in the context of the invention are, for example, organicsubstances which are capable of absorbing ultraviolet radiation and ofreleasing the energy absorbed in the form of longer-wave radiation, forexample heat. UV-B filters can be oil-soluble or water-soluble. Thefollowing are examples of oil-soluble substances:

3-benzylidene camphor and derivatives thereof, for example3-(4-methylbenzylideneycamphor;

4-aminobenzoic acid derivatives, preferably 4-(dimethylamino)-benzoicacid-2-ethylhexyl ester, 4-(dimethylamino)-benzoic acid-2octyl ester and4-(dimethylamino)-benzoic acid amyl ester;

esters of cinnamic acid, preferably 4-methoxycinnamic acid-2-ethylhexylester, 4-methoxycinnamic acid isopentyl ester, 2-cyano-3-phenylcinnamicacid-2-ethylhexyl ester (Octocrylene);

esters of salicylic acid, preferably salicylic acid-2-ethylhexyl ester,salicylic acid4-isopropylbenzyl ester, salicylic acid homomenthyl ester;

derivatives of benzophenone, preferably2-hydroxy-4-methoxybenzo-phenone,2-hydroxy4-methoxy4′-methylbenzophenone,2,2′-dihydroxy-4-methoxybenzophenone;

esters of benzalmalonic acid, preferably 4-methoxybenzalmalonic aciddi-2-ethylhexyl ester;

triazine derivatives such as, for example,2,4,6-trianilino-(p-carbo-2′-ethyl-1′-hexyloxy)-1,3,5-triazine and OctylTriazone;

propane-1,3-diones such as, for example,1-(4-tert.butylphenyl)-3-(4′-methoxyphenylypropane-1,3-dione;

Suitable water-soluble substances are

2-phenylbenzimidazole-5-sulfonic acid and alkali metal, alkaline earthmetal, ammonium, alkylammonium, alkanolammonium and glucammonium saltsthereof;

sulfonic acid derivatives of benzophenone, preferably2-hydroxy4-methoxybenzophenone-5-sulfonic acid and salts thereof;sulfonic acid derivatives of 3-benzylidene camphor such as, for example,4-(2-oxo-3-bomylidenemethyl)-benzene sulfonic acid and2-methyl-5-(2-oxo-3-bornylidene)-sulfonic acid and salts thereof.

Typical UV-A filters are, in particular, derivatives of benzoyl methanesuch as, for example1-(4′-tert.butylphenyl)-3-(4′-methoxyphenyl)-propane- 1,3-dione or1-phenyl-3-(4′-isopropylphenyl)-propane-1,3-dione. The UV-A and UV-Bfilters may of course also be used in the form of mixtures. Besides thesoluble substances mentioned, insoluble pigments, i.e. finely dispersedmetal oxides or salts, for example titanium dioxide, zinc oxide, ironoxide, aluminium oxide, cerium oxide, zirconium oxide, silicates(talcum), barium sulfate and zinc stearate, may also be used for thispurpose. The particles should have a mean diameter of less than 100 nm,preferably between 5 and 50 nm and more preferably between 15 and 30 nm.They may be spherical in shape although ellipsoidal particles or othernon-spherical particles may also be used. Besides the two groups ofprimary UV filters mentioned above, secondary UV filters of theantioxidant type may also be used. Secondary UV filters of theantioxidant type interrupt the photochemical reaction chain which isinitiated when UV rays penetrate into the skin. Typical examples areSuperoxid-Dismustase, tocopherols (vitamin E) and ascorbic acid (vitaminC).

In addition, hydrotropes such as, for example, ethanol, isopropylalcohol or polyols may be used to improve flow behavior. Suitablepolyols preferably contain 2 to 15 carbon atoms and at least twohydroxyl groups. Typical examples are

glycerol;

alkylene glycols such as, for example, ethylene glycol, diethyleneglycol, propylene glycol, butylene glycol, hexylene glycol andpolyethylene glycols having an average molecular weight of 100 to 1,000dalton;

technical oligoglycerol mixtures with a degree of self-condensation of1.5 to 10 such as, for example, technical diglycerol mixtures with adiglycerol content of 40 to 50% by weight;

methylol compounds such as, in particular, trimethylol ethane,trimethylol propane, trimethylol butane, pentaerythritol anddipentaerythritol;

lower alkyl glucosides, particularly those containing 1 to 8 carbonatoms in the alkyl group, for example methyl and butyl glucoside;

sugar alcohols containing 5 to 12 carbon atoms such as, for example,sorbitol or mannitol;

sugars containing 5 to 12 carbon atoms such as, for example, glucose orsucrose and

aminosugars such as, for example, glucamine.

Suitable preservatives are, for example, phenoxyethanol, formalde-hydesolution, parabens, pentanediol or sorbic acid. Suitable insectrepellents are N,N-diethyl-m-toluamide, pentane-1,2-diol or InsectRepellent 3535. A suitable self-tanning agent is dihydroxyacetone.

Examples of perfume oils include the extracts of blossoms (lavender,rose, jasmine, neroli), stems and leaves (geranium, patchouli,petitgrain), fruits (anise, coriander, caraway, juniper), fruit peel(bergamot, lemon, orange), roots (nutmeg, angelica, celery, cardamon,costus, iris, calmus), woods (sandalwood, pockwood, cedarwood,rosewood), herbs and grasses (tarragon, lemon grass, sage, thyme),needles and, branches (spruce, fir, pine, dwarf pine), resins andbalsams (galbanum, elemi, benzoin, myrrh, olibanum, opoponax). Animalraw materials, for example musk, civet and beaver, may also be used.Suitable synthetic and semisynthetic perfume oils are Ambroxan, eugenol,isoeugenol, citronellal, hydroxycitronellal, geraniol, citronellol,geranyl acetate, citral, ionone and methyl ionone.

Suitable dyes are any of the substances suitable and approved forcosmetic purposes as listed, for example, in the publication“Kosmetische Fäirbemittell” of the Farbstoffkommission der DeutschenForschungs-gemeinschaft, Verlag Chemie, Weinheim, 1984, pages 81 to 106.These dyes are normally used in concentrations of 0.001 to 0.1% byweight, based on the mixture as a whole.

The total percentage content of auxiliaries and additives may be from 1to 50% by weight and is preferably from 5 to 40% by weight, based on theparticular composition. The compositions may be prepared by 15 standardcold or hot processes and are preferably produced by the phase inversiontemperature method.

EXAMPLES Production Example

In a 2-liter three-necked flask equipped with a stirrer, dropping funneland distillation head, 540 g (2 moles) of partly hydrogenated tallowacid, 292 g (2 moles) of adipic acid and 2 g of sodium hypophosphitewere mixed at 80° C. A vacuum of 20 mm Hg was applied and 596 g (4moles) of triethanolamine were added in portions. The mixture was heatedto 170° C., the pressure was reduced to 5 mm Hg and water was removedfrom the equilibrium until the acid value had fallen to below 5. 500 gof the resulting ester (corresponding to 1.5 equivalents) weretransferred to a second flask and dissolved at 50° C. in 171 g ofisopropyl alcohol. 180 g (1.43 moles) of dimethyl sulfate were slowlyadded to the mixture, followed by stirring for 5 hours at 65° C. Aviscous, clear liquid with a cationic surfactant content of 1.2 meqlgand a dry residue of 80.5% by weight was obtained. A 5% by weightsolution in water was clear and had a Gardner color standard numberof 1. The product is commercially obtainable under the name of DehyquartD 6003.

Application Examples

Seven detergent mixtures were prepared and tested for viscosity,stability in storage, solubility, dispersibility, softness and wetcombability. Viscosity was measured in a Brookfield RVF viscosimeter(spindle 1, 10 r.p.m.) both immediately after production and afterstorage for 4 weeks at 40° C. Solubility was visually evaluated afterproduction while dispersibility (i.e. the stability of the aqueouspreparations) was visually evaluated after 1 h. Softness was determinedby a panel of six experienced testers after forced application of thetest mixtures to cofton fabric. On a scale of (1) to (4), (1) means verysoft, (2) soft, (3) hard and (4) very hard. The results are expressed asthe average values of the panel from three test cycles. In order todetermine wet combability, the static charging between the fiberfilaments is determined before and after treatment with the testsolutions as a measure of combability. Mixtures 1 to 3 correspond to theinvention while mixtures C1 to C4 are intended for comparison. Theresults are set out in Table 1.

TABLE 1 Composition and performance (pH = 3.1) Composition/performance 12 3 C1 C2 C3 C4 Dehyquart 2.5 1.25 3.75 5.0 — — — D 6003 Dehyquart — — —— 5.0 — 2.5 AU 46¹⁾ Rewopal 2.5 3.75 1.25 — — 5.0 2.5 V 3340²⁾ Water to100 Viscosity [cps] immediately 14 12 18 22 25 25 23 after 4 w, 14 12 1825 27 25 25 40° C. Solubility Clear Clear Clear Clear Cloudy CloudyCloudy Dis- Clear Clear Clear Cloudy Cloudy Cloudy Cloudy persibilitySoftness 1.0 1.0 1.0 1.5 1.7 3.0 2.0 Wet combability [mV] before 64.259.0 61.2 60.5 61.1 60.8 59.9 after 20.1 18.7 21.3 30.0 31.1 59.3 44.7difference 44.1 40.3 39.8 31.5 30.0 1.5 15.2 ¹⁾Triethanolamine reactedwith 2 moles of partly hydrogenated palm acid, methyl-quaternized,methosulfate salt ²⁾Diethylenetriamine reacted with 2 moles of tallowacid, 7EO adduct.

What is claimed is:
 1. A detergent mixture comprising (a) an oligomericesterquat which is the product of the process which comprises reacting amixture of a mono-carboxylic acid and a dicarboxylic acid with analkanolamine to form an alkanolamine oligoester and reacting thealkanolamine oligoester with an alloiating agent and (b) the product ofthe process which comprises reacting an alkylene oxide and a fatty acidamidoamine, wherein the weight ratio of components (a) to (b) is fromabout 10:90 to about 90:10; and wherein the oligomeric esterquat has atleast two cationic centers.
 2. The detergent mixture of claim 1 whereinthe carboxylic acids used to make the oligomeric esterquat have fromabout 6 to about 22 carbon atoms.
 3. The detergent mixture of claim 2wherein the dicarboxylic acid is adipic acid.
 4. The detergent mixtureof claim 1 wherein the mole ratio of the mono-carboxylic acids to thedicarboxylic acids in the oligomeric esterquat is from about 1:1 toabout 3:1.
 5. The detergent mixture of claim 1 wherein the alkanolamineis triethanolamine.
 6. the detergent mixture of claim 1 wherein themolar ratio of the mixture of mono-carboxylic acid and a dicarboxylicacid to the alkanolamine is from about 1:1 to about 3:1.
 7. Thedetergent mixture of claim 1 wherein component (a) is a compound of theformula (I):

wherein R¹CO is an aliphatic, linear or branched, saturated orunsaturated acyl group having from about 6 to about 22 carbon atoms, R²is an alkyl group having from 1 to 4 carbon atoms, each of R³ and R⁵ isan alkyl or hydroxyalkyl group having from 1 to 4 carbon atoms, R⁴ ishydrogen or R¹CO as defined above; each of n1, n2, n3 and n4 has a valueof from 1 to 5 and m has a value of from 1 to
 10. 8. The detergentmixture of claim 7 wherein R¹CO is a linear saturated acyl group havingfrom about 12 to about 18 carbon atoms, R² is a methyl group, R³ and R⁵are each hydroxyethyl groups, R⁴ is R¹CO as defined above; each of n1,n2, n3 and n4 has a value of 2 and m has a value of
 4. 9. The detergentmixture of claim 1 wherein component (b) is a compound of the formula(II):

wherein R⁶CO is an aliphatic, linear or branched, saturated orunsaturated acyl group having from about 6 to about 22 carbon atoms;each of R⁷and R⁸ is independently hydrogen or a hydroxy-substitutedalkyl group having from 1 to 4 carbon atoms; R⁹ is hydrogen, an alkylgroup having from 1 to 4 carbon atoms or R⁶CO as defined above; each ofR¹⁰ and R¹¹ is hydrogen or a methyl group, A is a linear or branchedalkylene group having from 2 to 4 carbon atoms, each of p and q has avalue of from 1 to 3; y has a value of from 1 to 3 and z has a value offrom 1 to
 20. 10. The detergent mixture of claim 9 wherein component (b)is a compound of the formula (II) wherein R⁶CO is a linear saturatedacyl group having from about 12 to about 18 carbon atoms; each of R⁷,R⁸, R¹⁰ and R¹¹ is hydrogen; R⁹ is R⁶CO as defined above; A is anethylene group, p and q each have a value of 2, y has a value of 1 and zhas a value of from 5 to
 10. 11. The detergent mixture of claim 1wherein component (a) is a compound of the formula (I):

wherein R¹CO is an aliphatic, linear or branched, saturated orunsaturated acyl group having from about 6 to about 22 carbon atoms, R²is an alkyl group having from 1 to 4 carbon atoms, each of R³ and R⁵ isan alkyl or hydroxyalkyl group having from 1 to 4 carbon atoms, R⁴ ishydrogen or R¹CO as defined above; each of n1, n2, n3 and n4 has a valueof from 1 to 5 and m has a value of from 1 to 10, and component b) is acompound of the formula (II):

wherein R⁶CO is an aliphatic, linear or branched, saturated orunsaturated acyl group having from about 6 to about 22 carbon atoms;each of R⁷and R⁸ is independently hydrogen or a hydroxy-substitutedalkyl group having from 1 to 4 carbon atoms; R⁹ is hydrogen, an alkylgroup having from 1 to 4 carbon atoms or R⁶CO as defined above; each ofR¹⁰ and R¹¹ is hydrogen or a methyl group, A is a linear or branchedalkylene group having from 2 to 4 carbon atoms, each of p and q has avalue of from 1 to 3; y has a value of from 1 to 3 and z has a value offrom 1 to
 20. 12. The detergent mixture of claim 11 wherein in componenta) R¹CO is a linear saturated acyl group having from about 12 to about18 carbon atoms, R² is a methyl group, R³ and R⁵ are each hydroxyethylgroups, R⁴ is R¹CO as defined above; each of ni, n2, n3 and n4 has avalue of 2 and m has a value of 4; and wherein component (b) is acompound of the formula (II) wherein R⁶CO is a linear saturated acylgroup having from about 12 to about 18 carbon atoms; each of R⁷, R⁸, R¹⁰and R¹¹ is hydrogen; R⁹ is R⁶CO as defined above; A is an ethylenegroup, p and q each have a value of 2, y has a value of 1 and z has avalue of fom 5 to 10.